EP4209519A1 - Procédé de préparation d'un copolymère d'eva à haute teneur en éthylène par polymérisation en solution sous une pression faible à moyenne - Google Patents

Procédé de préparation d'un copolymère d'eva à haute teneur en éthylène par polymérisation en solution sous une pression faible à moyenne Download PDF

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Publication number
EP4209519A1
EP4209519A1 EP23150280.8A EP23150280A EP4209519A1 EP 4209519 A1 EP4209519 A1 EP 4209519A1 EP 23150280 A EP23150280 A EP 23150280A EP 4209519 A1 EP4209519 A1 EP 4209519A1
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Prior art keywords
low
eva copolymer
ethylene
medium pressure
mass
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German (de)
English (en)
Inventor
Qian ZOU
Cunhao Zhang
Lei Chen
Iejun Riku
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Yunnan Zhengbang Technology Co Ltd
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Yunnan Zhengbang Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention belongs to the technical field of organic macromolecular compounds, and in particular, relates to a method for preparing an EVA copolymer with high ethylene content in a solution under a low to a medium pressure.
  • Ethylene vinyl acetate is a copolymer prepared by free radical polymerization of ethylene and vinyl acetate monomers.
  • EVA is the fourth major ethylene-containing polymer following low-density polyethylene (LDPE), high-density polyethylene (HDPE), and linear low-density polyethylene (LLDPE), and has a very important position in modern industry.
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • LLDPE linear low-density polyethylene
  • Ethylene and vinyl acetate can produce copolymers having different properties in different production processes.
  • a high-pressure and high-temperature polymerization device for the production of LDPE is utilized to carry out bulk free radical polymerization under high-pressure (1,000-3,000 bar) and high-temperature (150°C-200°C) conditions.
  • EVA Despite being a relatively mature technology for producing EVA with the vinyl acetate incorporation ranging from 5 to 40%, the capital costs are generally very high for the existing technology due to the high pressure and high temperature requirements for the operation. With physical properties such as high strength, high gloss, high transparency, and softness, the prepared EVA is generally applied in the fields of hot melt adhesives, shoemaking, foaming, injection molding, wires and cables, and food packaging. Especially, due to the development of photovoltaic industry in recent years, EVA has played a critical role in the field of photovoltaic films.
  • Ethylene and vinyl acetate can also undergo emulsion polymerization under low-pressure and low-temperature conditions to obtain a product that is generally called VAE copolymer in industry, and the content of VA in the VAE copolymer is generally more than 60%.
  • the VAE copolymer is generally applied in the form of emulsion or rubber resin. Due to its high VA content, the resulting copolymer is an elastomer, and thus is not applicable to the aforementioned application fields of the EVA copolymer.
  • CN106543343A discloses a method for preparing an EVA elastomer, whereby ethylene and vinyl acetate undergo free radical copolymerization in a solvent in a single reactor under the initiation of an initiator.
  • the process of free radical copolymerization includes stages of pre-polymerization, chain growth, and chain termination, which are performed at different temperatures, respectively, to prepare the EVA elastomer.
  • the temperature in the stage of pre-polymerization is controlled at 35°C-60°C; the temperature in the stage of chain growth is controlled at 55°C-75°C; and the temperature in the stage of chain termination is controlled at 45°C-70°C.
  • this patent application improves the amount of ethylene incorporated in EVA, which, however, is still below 40wt%. It is still not applicable to the aforementioned application fields of EVA copolymer.
  • the invention provides a method for preparing an EVA copolymer with an ethylene incorporation amount of more than 50wt% by means of a solution polymerization method under a low to a medium pressure and at low temperature.
  • the EVA copolymer prepared by this method has properties equivalent to those of an EVA copolymer obtained by conventional bulk polymerization at high temperature under high pressure, and is applicable to the application fields to which the EVA copolymer prepared using the conventional method is applicable. Meanwhile, the method also greatly reduces the equipment investment and the high-energy-consumption cost in production as compared with the conventional method for preparing the EVA at high temperature under high pressure.
  • the invention employs the following technical solutions.
  • a method for preparing an EVA copolymer with a high ethylene content by solution polymerization under a low to a medium pressure comprises the following steps: initiating with a free radical initiator(s), a copolymerization reaction between ethylene and vinyl acetate in a solvent in a reactor under a low to a medium pressure to obtain the EVA copolymer; and continuing to add ethylene during the reaction to maintain the low to medium pressure, wherein the low to medium pressure is between 1 MPa and 101 MPa, and a ratio of a mass of the vinyl acetate to a mass of the initially added ethylene is (1:1) to (1:20).
  • the pressure of the ethylene in the polymerization reaction system of the invention is controlled at 1 MPa (10 atmospheres) at minimum, and 101 MPa (1010 bar) at most.
  • the pressure of the ethylene may be kept constant, or varied with the progression of reaction.
  • excessively low pressure (below 1 MPa) of ethylene is unfavorable for the increase of a concentration of the ethylene in the reaction system, and it is certainly necessary to increase the amount of the solvent used.
  • the amount of the solvent used may be properly reduced, and meanwhile, the temperature for the polymerization reaction may be properly raised to accelerate the reaction so as to shorten a production cycle.
  • the initial concentration of the vinyl acetate in the reaction system has a great impact on the effective synthesis of EVA, and the ratio of the mass of the vinyl acetate to the initial mass of the ethylene requires to be controlled within the range from 1:1 to 1:20.
  • the ratio of the mass of the vinyl acetate to the initial mass of the ethylene added is too small, the polymerization reaction is slow, and it is difficult to initiate initial polymerization; slow reaction will also affect the feasibility of industrial production; and when the ratio is too big, the amount of the ethylene incorporated in the copolymer is greatly reduced, and the desired EVA cannot be synthesized.
  • the method of the invention has no limit on the polymerization temperature, for which, however, the optimum temperature should be selected according to the selected solvent and the pressure of ethylene condition. High polymerization temperature may increase the polymerization rate. Along with different polymerization temperatures, different free radical initiators should be selected to ensure the availability of sufficient concentration of free radicals.
  • the low to medium pressure is between 4 MPa and 95 MPa, more preferably, between 4 MPa and 81 MPa, further more preferably between 6 MPa and 20 MPa.
  • the ratio of the mass of the vinyl acetate to the mass of the initially added ethylene is (1:1) to (1:10).
  • the mass of the vinyl acetate added does not exceed 50% of the total mass of all monomers added.
  • the vinyl acetate monomer may be pre-added to the reactor, or dropwise added during the reaction.
  • the amount of the ethylene incorporated in the EVA greatly decreases, and may even decrease to below 50wt%.
  • the ratio of the mass of the vinyl acetate to the mass of the initially added ethylene is (1:2.5) to (1:8.5).
  • the mass of the vinyl acetate added does not exceed 30% of the total mass of all monomers added.
  • the mass of the free radical initiator(s) is 0.05% to 1% of the total mass of all monomers.
  • the mass of free radical initiator(s) is 0.1% to 0.6% of the total mass of all monomers.
  • the method further comprises the step of adding a third monomer to a reaction system, wherein the third monomer is one or more selected from olefins, acrylates, methacrylates, unsaturated acids, and acrylonitrile;
  • the olefins comprise propylene, n-butene, 1-hexene, 1,5-dihexene, 1-octene, 1,7-dioctene, and vinyl chloride;
  • the acrylates comprise methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate;
  • the methacrylates comprise methyl methacrylate, ethyl methacryl
  • the third monomer may be added at an early stage of the polymerization reaction or during polymerization to adjust the material properties of a polymerization product.
  • the addition of a difunctional or multifunctional monomer available for free radical polymerization can increase the molecular weight of the EVA copolymer and adjust the melt index of the same.
  • the solvent is one or more selected from C1-C6 alcoholic solvents, C1-C6 alcohol and water mixture, supercritical CO 2 , saturated aliphatic solvents, halogenated hydrocarbon solvents, naphthenic hydrocarbon solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents, aldehyde solvents, furan solvents, as well as acetic acid, ether, triethylamine, n-butyl mercaptan;
  • the C1-C6 alcoholic solvents comprise methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, isobutanol, n-pentanol, and n-hexanol;
  • the saturated aliphatic solvents comprise n-pentane, hexane, n-heptane, n-octane, n-decane, n-dodecane, and
  • the solvent selected in the invention is preferably a good solvent for the ethylene monomer, in order to increase the initial concentration of the ethylene monomer in the reaction system.
  • the selected good solvent for the ethylene can greatly decrease the requirement of the reaction system for the pressure of the ethylene, under the same condition.
  • the method further comprises the step of adding a chain transfer agent to the reaction system, wherein the chain transfer agent is lauryl mercaptan and/or mercaptoethanol.
  • a chain transfer agent is lauryl mercaptan and/or mercaptoethanol.
  • the free-radical chain transfer agent may be added at the early stage of the polymerization reaction or during the polymerization, in order to control the molecular weight and melt index of the EVA copolymer.
  • the free radical initiator is an azo initiator and/or a peroxide initiator.
  • the azo and/or peroxide initiator(s) commonly used in the market such as perester, perketal, peroxyketone, percarbonate, di-tert-butyl peroxide, isopropylbenzene peroxide neodecanoate, and tert-amyl perpivalate, may be selected as the free radical initiator.
  • the free radical initiator Before being added to the reaction system, the free radical initiator may be dissolved in the vinyl acetate monomer or solvent, such as vinyl acetate or ethyl acetate.
  • the percent content by mass of the ethylene in the EVA copolymer is ⁇ 50%.
  • the percent content by mass of the ethylene in the EVA copolymer is ⁇ 65%.
  • the percent content by mass of the ethylene in the EVA copolymer is ⁇ 70%.
  • the invention has the following beneficial effects: the amount of ethylene incorporated into the EVA copolymer prepared with the method of the invention is ⁇ 50wt%, and the EVA copolymer has properties equivalent to those of an EVA copolymer obtained by bulk polymerization at high temperature under high pressure, and is applicable to application fields to which the EVA copolymer prepared with a conventional method is applicable. Meanwhile, compared with the conventional method for preparing EVA at high temperature under high pressure, the method according to the invention also greatly reduces the equipment investment and the high energy-consumption cost during production.
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 1050 g of tert-butanol, 175 g of vinyl acetate, and 2.99 g of azobisisobutyronitrile (AIBN) initiator were added under vacuum, and after all components were added, the reactor was continuously evacuated three times with nitrogen for replacement.
  • ethylene was added while the system is heated up to 64°C and the reaction pressure rose to 6 MPa.
  • the amount of the ethylene added was 525 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1:3).
  • ethylene was then added continuously to maintain the pressure of ethylene at 6 MPa throughout the 12 h reaction time, and the temperature was controlled at 64°C during the reaction; and after the reaction started, 1.68 g of AIBN initiator (10wt%) dissolved in ethyl acetate was continuously added. After 12 hours of reaction, the total amount of ethylene added was 724 g.
  • the reactor was depressurized 12 h after the reaction, 1 g of sorbic acid was added to terminate the polymerization reaction, and then the resulting polymer was discharged.
  • the polymer had a solid content of 26.05%, with a theoretical solid content of 46.13%, and a monomer conversion rate was 56.47%.
  • the incorporation amount of ethylene was 70% as measured with the FTIR method, and a melt flow index at 219 g/10 min (190°C/2.16 kg).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen o remove moisture and oxygen in the reactor.
  • the reactor was provided with a mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 439 g of cyclohexane, 330 g of vinyl acetate, 50 g of methacrylic acid, and 2.82 g of AIBN initiator were introduced under vacuum, and after all components were added, the reactor was evacuated three times with nitrogen for replacement.
  • ethylene was added while the system was heated to 64°C and the reaction pressure rose to 6 MPa.
  • the amount of the ethylene added was 601 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1:1.82).
  • ethylene was then added continuously to maintain the pressure of ethylene at 6 MPa throughout the 12 h reaction time, and the temperature was controlled at 64°C during the reaction; and after the reaction started, 0.79 g of AIBN initiator (10wt%) dissolved in ethyl acetate was continuously added. After 12 hours of reaction, the total amount of ethylene added was 701 g.
  • the reactor was depressurized 12 h after the reaction, 1 g of sorbic acid was added to terminate the polymerization reaction, and then the resulting polymer was discharged.
  • the polymer had a solid content of 48.23%, with a theoretical solid content of 70.10%, and a monomer conversion rate was 68.80%.
  • the incorporation amount of ethylene was 55.6% as measured with the FTIR method, and a melt flow index at 300 g/10 min (190°C/2.16 kg).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 800 g of xylene, 300 g of vinyl acetate, and 1 g of AkzoNobel Trigonox ® 42S (tert-butyl peroxy-3,5,5-trimethylhexanoate) initiator were introduced under vacuum, and after all components were added, the reactor was evacuated three times with nitrogen for replacement. Then, ethylene was added while the system was heated to 125°C and the reaction pressure rose to 15.2 MPa.
  • the amount of the ethylene added was 755 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1 :2.52). Taking the temperature reaching 125°C as the start of the reaction, ethylene was then added continuously to maintain the pressure of ethylene at 15.2 MPa to react for 5 h, and the temperature was controlled at 125°C during the reaction. After 5 hours of reaction, the total amount of ethylene added was 873 g. The reactor was depressurized 5 h after the reaction, and cooled to room temperature, and then the resulting polymer was discharged. The polymer had a solid content of 38.00%, with a theoretical solid content of 52.70%, and a monomer conversion rate was 72.11%. The incorporation amount of ethylene was 65% as measured with the FTIR method, and a melt flow index at 55 g/10 min (190°C/2.16 kg).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 875 g of diethyl carbonate, 175 g of vinyl acetate, 25 g of propylene, and 2.99 g of AIBN initiator were added under vacuum, and after all components were added, the reactor was evacuated three times with nitrogen for replacement.
  • ethylene was added while the system was heated to 64°C and the reaction pressure rose to 6 MPa.
  • the amount of the ethylene added was 543 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1:3.1).
  • ethylene was then added continuously to maintain the pressure of ethylene at 6 MPa to react for 12 h, and the temperature was controlled at 64°C during the reaction; and after the reaction started, 1 g of AIBN initiator (10wt%) dissolved in ethyl acetate was continuously added. After 12 hours of reaction, the total amount of ethylene added was 695 g.
  • the reactor was depressurized 12 h after the reaction, 1 g of sorbic acid was added to terminate the polymerization reaction, and then the resulting polymer was discharged.
  • the polymer had a solid content of 30.00%, with a theoretical solid content of 50.00%, and a monomer conversion rate was 60.00%.
  • the incorporation amount of ethylene was 65% as measured with the FTIR method, and a melt index at 118 g/10 min (190°C/2.16 kg).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 439 g of tert-butanol, 330 g of vinyl acetate, and 1.41 g of AIBN initiator were added under vacuum, and after all components were added, the reactor was evacuated three times with nitrogen for replacement.
  • ethylene was added while the system was heated to 64°C and the reaction pressure rose to 6 MPa.
  • the amount of the ethylene added was 612 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1:1.85).
  • ethylene was then added continuously to maintain the pressure of ethylene at 8 MPa to react for 12 h, and the temperature was controlled at 64°C during the reaction; and after the reaction started, 1 g of AIBN initiator (10wt%) dissolved in ethyl acetate was continuously added. 1.5 g of lauryl mercaptan as the chain transfer agent was added 3 hours after the start of reaction. After 12 hours of reaction, the total amount of ethylene added was 775 g. The reactor was depressurized 12 h after the reaction, 1 g of sorbic acid was added to terminate the polymerization reaction, and then the resulting polymer was discharged.
  • the polymer had a solid content of 57.64%, with a theoretical solid content of 71.50%, and a monomer conversion rate was 80.62%.
  • the incorporation amount of ethylene was 58% as measured with the FTIR method, and a melt flow index at 35 g/10 min (190°C/2.16 kg).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 1050 g of tetrahydrofuran, 100 g of vinyl acetate, and 2.99 g of AIBN initiator were added under vacuum, and after all components were added, the reactor was evacuated three times with nitrogen for replacement.
  • ethylene was added while the system was heated to 64°C and the reaction pressure rose to 8 MPa.
  • the amount of the ethylene added was 850 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1:8.5).
  • ethylene was then added continuously to maintain the pressure of ethylene at 8 MPa to react for 12 h, and the temperature was controlled at 64°C during the reaction; and after the reaction started, 1.68 g of AIBN initiator (10wt%) dissolved in ethyl acetate was continuously added. After 12 hours of reaction, the total amount of ethylene added was 990 g. After 12 hours of reaction, the reactor was depressurized 12 h of reaction, 1 g of sorbic acid was added to terminate the polymerization reaction, and then the resulting polymer was discharged. The polymer had a solid content of 22.00%, with a theoretical solid content of 50.90%, and a monomer conversion rate was 43.22%. The incorporation amount of ethylene was 78% as measured with the FTIR method, and a melt flow index at 400 g/10 min (190°C/2.16 kg).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a magnetic drive mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 80 g of n-pentane, 30 g of vinyl acetate were added under vacuum, and after all components were added, the reactor was evacuated three times with nitrogen for replacement.
  • ethylene was added while the system was heated to 150°C and the reaction pressure rose to 27 MPa.
  • the amount of the ethylene added was 93 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1: 3.1).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a magnetic drive mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 50 g of vinyl acetate was added under vacuum, followed by 50 g of CO 2 gas.
  • ethylene was added while the system was heated to 125°C and the reactor pressurized to 64 MPa.
  • the amount of the ethylene added was 132 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1: 2.6).
  • the method for preparing the EVA copolymer with high ethylene content by polymerization in solution under a low to a medium pressure was as follows.
  • a 5 L high-pressure stainless-steel reactor was evacuated three times with nitrogen to remove moisture and oxygen in the reactor.
  • the reactor was provided with a magnetic drive mechanical stirrer, temperature and pressure measuring devices, and a feeding port.
  • 30 g of vinyl acetate was added under vacuum, followed by 150 g of dimethyl carbonate.
  • ethylene was added while the system was heated to 125°C and the reactor pressurized to 99 MPa.
  • the amount of the ethylene added was 148 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene was 1: 4.9).
  • the method for preparing the EVA copolymer by polymerization in solution under a low to a medium pressure was basically the same as that in Example 1, except that the temperature for the polymerization reaction was controlled at 64°C, and the pressure of ethylene during the reaction was kept at 0.5 MPa.
  • the resulting polymer had a solid content of 35.82%, with a theoretical solid content of 57.20%, and a monomer conversion rate was 62.62%.
  • the incorporation amount of ethylene was 7.2% as measured with the FTIR method.
  • the melt index and other properties were not measured since the amount of ethylene incorporated in the EVA polymer prepared in this comparative example was too low.
  • the method for preparing the EVA copolymer by polymerization in solution under a low to a medium pressure was basically the same as that in Example 1, except that the amount of the vinyl acetate added is 1250 g, the amount of the ethylene added was 756 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene is 0.60:1) when the reaction temperature rose to 64°C, and the total amount of the ethylene added was 806 g after 12 hours of reaction.
  • the resulting polymer had a solid content of 52.92%, with a theoretical solid content of 66.69%, and a monomer conversion rate was 79.35%.
  • the incorporation amount of ethylene was 27% as measured with the FTIR method.
  • the melt index and other properties were not measured since the amount of ethylene incorporated in the EVA polymer prepared in this comparative example did not meet requirements.
  • the method for preparing the EVA copolymer by polymerization in solution under a low to a medium pressure was basically the same as that in Example 1, except that 3000 g of tert butanol was added; the amount of the vinyl acetate added was 50 g; the amount of the ethylene added was 1200 g (the ratio of the mass of the vinyl acetate to the initial mass of the ethylene is 1:24) when the reaction temperature rose to 64°C; and the total amount of the ethylene added is 1300 g after 12 hours of reaction.
  • the resulting polymer had a solid content of 2.5%, with a theoretical solid content of 31.00%, and a monomer conversion rate was 8.06%.
  • the incorporation amount of ethylene was 85% as measured with the FTIR method. Since the monomer conversion rate in this comparative example was excessively low, the yield of the prepared EVA copolymer was too low to be used for measuring the property indexes.
  • the object of the invention to reduce the production cost and improve the ethylene incorporation in EVA at the same time cannot be achieved; and the waste raw materials can also cause a burden on environmental management.
  • the amount of the ethylene incorporated in the EVA copolymer prepared is greatly reduced, such that the EVA copolymer cannot be used in the fields where the EVA copolymer prepared at high temperature and under high pressure in a conventional way is used.

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EP23150280.8A 2022-01-07 2023-01-04 Procédé de préparation d'un copolymère d'eva à haute teneur en éthylène par polymérisation en solution sous une pression faible à moyenne Pending EP4209519A1 (fr)

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WO2020175188A1 (fr) * 2019-02-26 2020-09-03 株式会社Moresco Procédé de fabrication d'adhésif thermofusible à base d'acétate de vinyle-éthylène, et adhésif thermofusible
CN114230700B (zh) * 2022-01-07 2022-10-04 云南正邦科技有限公司 一种中低压溶液聚合制备高乙烯含量eva共聚物的方法
CN115197354B (zh) * 2022-07-22 2023-02-10 云南正邦科技有限公司 一种低压聚合eva溶剂循环使用的方法及系统
CN115322703B (zh) * 2022-08-30 2023-06-16 江阴伟韬塑料新材料有限公司 一种热熔胶膜及其制备方法
CN116003661A (zh) * 2022-12-08 2023-04-25 云南正邦科技有限公司 一种制备高乙烯含量的eva共聚物的方法

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